JPH01229694A - Optical data recording medium - Google Patents

Abstract

PURPOSE:To obtain an optical data recording medium having an org. dye recording layer excellent in heat and light stability and improved in regenerative deterioration, by containing at least one specific compound in a recording layer. CONSTITUTION:At least one kind of a compound selected from ones represented by formulae (I), (II) is contained in the recording layer of an optical data recording medium. In the aforementioned formulae, R1-R4 are a 1-12C alkyl group which may be substituted or hydrogen, R5 is a 1-12C alkyl group which may be substituted, an alkoxy group, a hydroxyl group, halogen or hydrogen, Z is an atom group necessary for completing a 5- or 6-membered carbocyclic ring, l is 0 or 1 and X is a metal complex anion. The above-mentioned purpose is achieved by containing at least one kind of a compound selected from ones represented by formulae (III), (IV) (wherein X is an acid anion) in the recording layer containing an org. dye based on a polymethine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an improved optical information recording medium that can be used in the optical recording field.

[Prior art]

Until now, optical information recording media have been proposed in which a recording layer made of a low melting point metal or a low melting point metal and a dielectric is provided on a substrate, but these have poor storage stability, low resolution, and recording density. It has disadvantages such as low yield, difficult manufacturing conditions, and high cost. Therefore, it has recently been proposed to use an organic dye thin film as the recording layer in place of the metal thin film. This organic dye thin film has a low melting point, low decomposition temperature, and low thermal conductivity, so it has the potential for high sensitivity and high density, and because film formation can be done by coating, it is highly mass-producible and expected to be low cost. There are advantages such as being able to

Conventionally, it has been known to use a film of a polymethine compound such as a cyanine dye or a merocyanine dye as the organic dye film. However, recording layers composed of such dyes have poor heat and light stability, have problems with storage stability, and are susceptible to playback deterioration. An object of the present invention is to provide an optical information recording medium having an organic dye recording layer with excellent properties and improved reproduction deterioration.

〔composition〕

The above object is achieved by containing at least one compound selected from the following general formulas (1) and (II) in the recording layer of the optical information recording medium (invention of claim (1)).

General formula (I): (In the above formula, R1-R4 are optionally substituted alkyl groups having 1 to 12 carbon atoms or hydrogen, and R9 is hydrogen having 1 to 12 carbon atoms.
(optionally substituted alkyl group, alkoxy group, hydroxyl group, halogen or hydrogen, 2 is an atomic group necessary to complete a 5- or 6-membered carbon ring, AIto or 1, X represents a metal complex anion) Further, the above object is to contain at least one compound selected from the following general formulas (III) and (IV) in the recording layer containing an organic dye containing a polymethine compound as a main component in an optical information recording medium. This is achieved by (
invention of claim (2)).

General formula (■) 2 General formula (■): (In the above formula, R1-R4 are optionally substituted alkyl groups having 1 to 12 carbon atoms or hydrogen, and R9 is hydrogen having 1 to 12 carbon atoms.
an optionally substituted alkyl group, alkoxy group, hydroxyl group, halogen or hydrogen, Z is an atomic group necessary to complete a 5- or 6-membered carbon ring, Ω is 0 or 1, and X represents an acid anion. ) The optical information recording medium of the present invention can be produced basically by providing a recording layer containing at least one compound selected from the above general formulas (1) and (II) on a substrate, or by providing a recording layer containing at least one compound selected from the above general formulas (1) and (II), or a polymethine compound. It is constituted by providing a recording layer containing an organic dye having as a main component and at least one compound selected from the above general formulas (f[I) and (IV). A subbing layer can be provided between the substrate and the recording layer, or a protective layer can be provided on the recording layer. Alternatively, the pair of recording media configured in this manner may be formed into an air-sand weasel structure in which the recording layer is placed inside and sealed with another substrate through a space, or a close-contact sand-in structure in which the recording layer is placed inside and the other substrate is sealed through a space. pasting)
It may be a structure.

Next, the materials constituting the optical information recording medium of the present invention and the necessary characteristics of each layer will be specifically explained.

(1) Substrate As a necessary characteristic of the substrate, it must be transparent to the laser beam used only when recording and reproducing is performed from the substrate side, and it does not need to be transparent when recording and reproducing is performed from the recording layer side. As the substrate material, for example, plastics such as polyester, acrylic resin, polyamide, polyolefin resin, phenol resin, epoxy resin, polyimide, glass, ceramic, or metal can be used.

Note that a preformat such as an address signal or a pregroove for a guide groove may be formed on the surface of the substrate.

(2) Recording layer The recording layer causes some optical change by irradiation with a laser beam and can record information by that change. It consists of at least one type of polymethine compound selected from (1) and (II).

Here, specific examples of the cation of the polymethine compound preferably used in the invention of claim (1) are shown below, but the invention is not limited thereto.

Table 2 Further, specific examples of metal complex anions preferably used in the invention of claim (1) are shown below, but the invention is not limited thereto.

(In the above formula, N is Ni, Pd or Pt, R, ~R4
represents hydrogen, halogen, or a substituted or unsubstituted alkyl group, alkoxy group, or amino group) (In the above formula, R6 to R represent hydrogen, a cyano group, or a substituted or unsubstituted alkyl group or aryl group, and each may be the same or different) (E) (In the above formula, R9 to R1□ are hydrogen, halogen, or a substituted or unsubstituted alkyl group, alkoxy group, or amino group, R□, R1, (represents hydrogen, a cyano group, or a substituted or unsubstituted alkyl group or aryl group, which may be the same or different from each other, and the above aromatic ring may be fused with another aromatic ring) (F) (In the above formula, l'+is~R□. represents hydrogen, halogen, or a substituted or unsubstituted alkyl group, alkoxy group, or amino group, and may be the same or different from each other) ( G) (In the above formula, R8-84 represents hydrogen, halogen, or a substituted or unsubstituted alkyl group, alkoxy group, or amino group, as in (C) above).

(In the above formula, R1N to R2° represent hydrogen, halogen, or a substituted or unsubstituted alkyl group, alkoxy group, or amino group, and may be the same or different from each other) Further, in the invention described in claim (2), the recording layer is made of an organic dye whose main component is a polymethine compound. In this case, the polymethine compound includes polymethine dyes, cyanine dyes, merocyanine dyes, croconium dyes, pyrylium dyes, etc., and specific examples thereof are described in, for example, JP-A-58-194595.

Then, in the recording layer, the general formula (III) and (rV)
It contains at least one compound selected from the following.

The weight ratio of the polymethine compound and the above compounds is 30 nia 0 ~
The ratio is 99:1, preferably 60:40 to 95:5.

Here, specific examples of compounds preferably used in the invention of claim (2) are shown below, but the invention is not limited thereto.

(J) Table 10 In order to improve recording characteristics and stability, the recording layer of the recording medium of the present invention may contain other dyes, such as phthalocyanine, tetrahydrocholine, dioxazine, triphetchazine, etc. dyes, phenanthrene-based, anthraquinone (indanthrene)-based, xanthine-based, triphenylmethane-based, triphenylamine-based, azulene-based dyes, and metals or metal compounds, such as In, Sn,
Te, Bi, AQ, As, Se, Tea,, SS
n01A, Cu, Cd, etc. may be mixed and dispersed,
It may also be laminated. In addition, the recording m can contain a polymeric material, a storage stabilizer (a metal complex, a phenolic compound), a dispersant, a flame retardant, a lubricant, a plasticizer, and the like. The film thickness of tUF is 100 to 10. , preferably 20
0 to 2 μ-. Methods for forming the recording layer include vapor deposition, CVO method, sputtering method, and solvent coating method, such as
Dip coating, spray coating, spinner coating, blade coating, roller coating, curtain coating, etc. can be used.

(3) Undercoat layer The undercoat layer (a) improves adhesion, (b) serves as a barrier against water or gas, (C) improves storage stability of the recording layer, and (d)
) Improvement of reflectance, (protection of substrate from eHa agent, (f)
Used for purposes such as forming pre-grooves. (a
), various polymer materials such as ionomer resins, polyamide resins, vinyl resins, natural resins, natural polymers, silicones, liquid rubbers, and silane coupling agents can be used. ,(b)
For the purpose of (c), inorganic compounds such as 5in2, MgF, 5iO1Tie2, etc.
, ZnO, TiN, SiN, etc. Metals or metalloids such as Zn, Cu, S, Ni, Cr, Ge, Se,
Au, Ag, AQ, etc. can be used. For the purpose of (d), metals such as AQ, Ag, etc. or organic thin films with metallic luster, such as methine dye 5.
Xanthine dyes etc. can be used, and (e) and (
For the purpose of f), ultraviolet curing resins, thermosetting resins,
Thermoplastic resin or the like can be used.

(4) Protective layer The protective layer is used for the purposes of (a) protecting the recording layer from scratches, dust, dirt, etc., (b) improving storage stability of the recording layer, and (C) improving reflectance. be done. For these purposes, the materials listed above for the undercoat layer can be used.

In the present invention, the undercoat layer and the protective layer may contain stabilizers, dispersants, flame retardants, lubricants, antistatic agents, surfactants, plasticizers, etc., as in the case of the recording layer. . Furthermore, the undercoat layer and the protective layer can also contain a polymethine compound.

〔effect〕

The optical information recording medium of the present invention configured as described above is capable of recording and reproducing using long wavelength light such as a semiconductor laser, has improved thermal stability and optical stability, and has excellent storage stability and playability. It has little deterioration. Furthermore, pits can be formed in a good shape and a high C ratio can be obtained.

〔Example〕

The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.

First, an embodiment of the invention of claim (1) will be described.

(Examples 1 to 7) Polymethyl methacrylate (PMMA) with a thickness of 1.2 m
On board (diameter 130ai), acrylic photopolymer depth 900 people, half value @ 0.4pm, pitch 1.6
A recording layer with a thickness of 700 mm was prepared by applying a compound consisting of the above-mentioned cation and above-mentioned anion as a 1,2-dichloroethane solution using a spinner onto a substrate on which μ- spiral groups were provided, and a recording medium was obtained. Ta.

Cation Anion Example L A-10C-1 2A-10D-7 3A-10E-11 4A-7D-5 5A-12C-1 6B-IG-1 7B-7D-9 (Example 8) Same as Example 1 After forming a recording layer of 500 layers, a silver vapor deposited film of 100 layers was further provided thereon to obtain a recording medium.

(Example 9) A Te vapor-deposited film with a thickness of 100 mm was provided on the polymethyl methacrylate substrate shown in Example 1, and a recording layer similar to that in Example 1 was further applied with a spinner to a thickness of 400 mm. Obtained a recording medium.

(Example 10) A recording medium was obtained in the same manner as in Example 1, except that a combination of the compound of Example 1 and the compound of Example 4 (weight ratio = 1:1) was used.

(Comparative Example 1) In Example 1, the anion was changed to Cl2 instead of C-1.
e.

(Comparative Example 2) In Example 1, the cation was replaced with N-(
Bu) 4.

(Comparative Example 3) In Example 1, the following compound was used as a recording material.

A semiconductor laser beam having a wavelength of 790 nm was applied to each recording medium obtained as described above from the substrate side at a recording frequency of 5.0 MHz.
Information was written and reproduced at a linear velocity of 2.1 m/see, and the reproduced waveform was subjected to spectrum analysis (scanning filter, bandwidth 30 kHz), and the C/N ratio was measured. Further, this same recording medium was irradiated with tungsten light of 54,000 lux for 20 hours to perform an accelerated reproduction deterioration test, and then the reflectance and C ratio were measured. In this case, the reflectance was measured from the substrate side.

The above measurement results are shown in the table below.

Next, an example of the invention of claim (2) will be shown.

(Example 11) Polymethyl methacrylate (PMMA) with a thickness of 1.2 em
) On a board (130 meters in diameter), a depth of 900 people, half width 0.4 m, pitch 1.6 I is made of acrylic photopolymer.
The above compound NG! was deposited on a substrate on which helical groups with a half value @0.4IJa and a pitch of 1.6 μl were provided. Example 12) In Example 11, the compound Nil-10 was used in place of the compound Ncil-12 in a 1,2-dichloroethane solution in a weight ratio of 1:1. A recording medium was obtained.

(Example 13) In Example 11, a recording medium was obtained using the compound Hal-13 instead of the compound Ncl-12.

(Example 14) In Example 11, tetrahydrofuran (T) IF) was used instead of 1,2-dichloroethane when the compound NG
The above compound 1-11 was used in place of I-12, and the following compound (II) was used in place of the above compound (1) 1'
A recording medium was obtained by mixing the compound NQT-11 and the following compound (II) in a weight ratio of 5:1.

(Example 15) In Example 14, a recording medium was obtained using the compound NαI-4 instead of the compound Na1-11.

(Example 16) In Example 14, a recording medium was obtained using the compound NaJ-3 instead of the compound NQI-11.

(Example 17) In Example 11, the substrate was an injection plate,
Te was deposited in a vacuum of 10-' Torr, and then the recording material of Example 11 was coated with a spinner as a methanol/ethylene dichloride (80:20) solution to obtain a recording medium with a thickness of 400 Torr. Ta.

(Example 18) In Example 17, a recording medium was obtained using the following compound (In) instead of the compound (1) and the compound Nn1-7 instead of the compound Nαl-12.

(Example 19) In Example 17, a recording medium was obtained using the following compound (IV) instead of the compound (1) and the compound N (11-7 instead of the compound NQI-12).

(Comparative Example 4) A recording medium was obtained in Example 11 using a recording layer containing only a polymethine dye.

(Comparative Example 5) A recording medium was obtained in Example 14 using a recording layer containing only the polymethine dye.

A semiconductor laser beam with a wavelength of 790 nm is applied to each recording medium obtained as described above from the substrate side at a recording frequency of 5. OMII
Information was written and reproduced at a linear speed of 2.1 m+/see, and the reproduced waveform was subjected to spectrum analysis (scanning filter, bandwidth 30 KHz), and the C/N ratio was measured.

Further, this same recording medium was subjected to an accelerated playback deterioration test by irradiating tungsten light of 1 V for 15 hours from a distance of 30°, and the reflectance and C/N ratio were measured. in this case,
The reflectance was measured from the substrate side.

The above 1illJ results will be shown to adults.

Claims (2)

[Claims] (1) In an optical information recording medium in which a recording layer is provided directly or via an undercoat layer on a substrate and further provided with a protective layer as necessary, the following general formulas (I) and (
An optical information recording medium containing at least one compound selected from II). General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R_1 to R_4 are substituted carbon atoms with 1 to 12 carbon atoms. optional alkyl group or hydrogen, R_5 has 1 carbon number
~12 optionally substituted alkyl groups, alkoxy groups, hydroxyl groups, halogen or hydrogen, Z is an atomic group necessary to complete a 5- or 6-membered carbon ring, n is 0 or 1, X
indicates a metal complex anion) (2) In an optical information recording medium in which a recording layer containing an organic dye mainly composed of a polymethine compound is provided on a substrate directly or via an undercoat layer, and a protective layer is further provided as necessary, in the recording layer. An optical information recording medium characterized in that the optical information recording medium contains at least one compound selected from the following general formulas (III) and (IV). General formula (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R_1 to R_4 are substituted carbon atoms with 1 to 12 carbon atoms) optional alkyl group or hydrogen, R_5 has 1 carbon number
~12 optionally substituted alkyl groups, alkoxy groups, hydroxyl groups, halogen or hydrogen, Z is an atomic group necessary to complete a 5- or 6-membered carbon ring, l is 0 or 1, X
indicates an acid anion)